Textile treating agents and methods of preparing same



United States Patent 3,503,701 TEXTILE TREATING AGENTS AND METHODS OF PREPARING SAME Giuliana C. Tesoro, Dobbs Ferry, N.Y., assignor to J. P. Stevens & Co., Inc., New York, N.Y., a corporation of Delaware No Drawing. Filed Nov. 15, 1965, Ser. No. 507,649 Int. Cl. D06m 13/12, 13/34 U.S. Cl. 8-116.3 3 Claims ABSTRACT OF THE DISCLOSURE This invention relates to a process for modifying a cellulosic textile which comprises the step of reacting said textile with an alkaline catalyst at temperatures in excess of 80 C. with solutions of aldehyde carbamate ketone condensates.

This invention relates to the treatment of cellulosic textile materials to produce textiles having improved properties. More particularly, this invention relates to the preparation of novel textile treating agents which impart to cellulosic textiles improved dimensional stability, crease recovery and fiat drying (wash/ wear) properties.

It is known to enhance the properties of cellulosic textile materials by treating them with polyfunctional chemical compounds, such compounds generally forming crosslinks between cellulosic chains. Many of these textile treating agents require acidic conditions in order for the reaction with cellulose to occur. Thus, for example, N-methylol derivatives of urea, of cyclic urea derivatives and of alkyl carbamates are effective crosslinking agents for cellulose when used in the presence of acidic or acid forming catalysts. It is often desirable, however, to prevent acidic substances from contacting either the textile fibers themselves or materials used to treat the fibers, such as dyestuffs, sizes, softeners, and the like. On the other hand, treatment of cellulosic textiles under alkaline conditions is not always satisfactory.

Polyfunctional N-methylol derivatives employed to crosslink cellulose under acidic conditions, react either incompletely or not at all when used under alkaline conditions. For example, N,N-dimethylol alkyl carbamates cannot be used to modify cellulose in the presence of alkaline catalysts since the resulting products exhibit several undesirable characteristics, including chlorine retention and susceptibility to chlorine damage upon washing with hypochlorite bleaching solutions. Crosslinking agents for cellulose which utilize alkaline conditions, such as the condensates of acetone with formaldehyde disclosed in U.S. Patent 2,711,971 and in British Patent 955,449, also exhibit a serious failing in that textiles treated with these agents either discolor immediately or upon subsev quent washing with alkaline solutions. Accordingly, there is a need for reagents which can react with cellulose under alkaline conditions but which avoid the shortcomings of the alkali catalyzed treatments heretofore known in the art.

It is an object of this invention to provide novel treating agents for the modification of cellulosic textiles.

It is another object of this invention to provide a method for modifying cellulosic textiles under alkaline conditions.

Another object of this invention is to provide modified cellulosic textiles which exhibit enhanced properties of dimensional stability, crease recovery, and flat drying, said properties being durable to laundering under alkaline conditions.

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Other objects and advantages of this invention will be apparent from the description that appears hereafter.

In accordance with this invention, novel textile treating agents are prepared by reacting in an alkaline medium formaldehyde with -a ketone having the formula CHgCOR where R is a straight or branched chain alkyl and preferably a lower alkyl having from 1 to 4 carbon atoms and with an alkyl carbamate having the formula O R() i NHz where R is a substituted or unsubstituted alkyl having from 1 to 6 carbon atoms. Suitable examples of R include methyl, ethyl, propyl, isopropyl, butyl, isobutyl and the like, and suitable examples of R include methyl, ethyl, propyl, isopropyl, butyl, hydroxyethyl, hydroxypropyl, alkoxyethyl, alkoxypropyl, and the like. The exact structure of these mixed condensation products is not known, but the condensates serve to impart desirable characteristics to cellulosic textiles under alkaline conditions, as will be shown hereinafter.

The mixed condensation product can be obtained by admixing the formaldehyde, ketone, and carbamate and carrying out the reaction between all of the reactants simultaneously, or the formaldehyde can first be reacted with one of the other reactants (e.g., the carbamate) and the resulting product reacted with the remaining reactant (e.g., the ketone). Alternatively, the formaldehyde can be reacted with mixtures of the ketone and the carbamate. Or, the condensation product can be prepared by mixing a reaction product of ketone and formaldehyde with a reaction product of carbamate and formaldehyde. All of the aforedescribed reactions must be carried out under alkaline conditions. It is quite evident, therefore, that several alternative procedures exist whereby the mixed condensation products of this invention can be obtained.

In general, the mole ratio of the reactants should be at least 2 moles of formaldehyde for each combined mole of the other reactants, i.e., for each mole of (ketone plus carbamate). It is preferred that the mole ratio of formaldehydezketone:carbamate range from 4: 1:1 to 6:1:1, although mole ratios not falling within this range nevertheless produce satisfactory products. It should be noted that the ratio of ketone to carbamate need not be 1:1 but can vary widely provided, of course, that the required ratio with formaldehyde is maintained. The condensation reaction is carried out at a pH ranging from about 8.0 to about 12.0 in either an aqueous or non-aque' ous medium. The temperature of the reaction may vary from about 0 C. to about C., and preferably from about 10 C. to about 30 C., while the reaction time will vary from about 1 hour to about 24 hours, depending upon the extent of reaction desired. It should be noted that, although the structures of the aforedescribed condensation products have not been determined, the products are not merely simple mixtures, but complex equilibria are probably established among various possible derivatives of the ketone and carbamate reactants.

As was mentioned previously, the condensation products of this invention are excellent agents for treating cellulose containing textile materials. In treating cellulosic textiles, a solution of the condensation product is applied to the textile by any conventional means such as by padding, dipping, spraying and the like. The treated textile is then dried and heated, in the presence of an alkaline catalyst, to complete the reaction. A particularly noteworthy feature of the textile treating agents of this invention is that they are stable in the presence of alkaline catalysts and do not react with a cellulosic substrate until heat is applied. It is thus possible to treat a cellulosic fabric with the new composition, dry the fabric, manufacture a garment from such treated fabric, and subsequently carry out reaction of the agent with cellulose, thereby setting the garment in a desired configuration. It is, of course, possible to impregnate a textile material with solutions of the formaldehyde, ketone, and carbamate reagents, and then maintain the impregnated material under wet reaction conditions to permit the reagents to react prior to their reaction with the textile.

In preparing the textile treating solutions, the mixed condensation product can be used in concentrations of from about 3% to about 30%, by weight, based on the weight of the textile being treated, with the preferred range being from 5% to 15%. Usually, the amount of agent will vary with the properties intended to be imparted to the textile. Thus, for example, quantities of treating agent ranging from about 3% to about 5% are generally suflicient to impart dimensional stability, but larger amounts would be required to impart wash and wear properties. The condensation products may be applied from either an aqueous or non-aqueous solution.

The alkaline catalyst employed in treating textile materials is preferably a weak base such as alkali metal acetates, carbonates or bicarbonates, but stronger bases such as alkali metal phosphates can be used. Strong bases such as alkali metal hydroxides and silicates can also be used as catalysts, but the amount of such catalyst must be carefully controlled in order to prevent degradation of the cellulose. When alkali metal carbonates or bicar bonates are employed to catalyze the reaction of the mixed formaldehyde-ketone-carbamate condensation products, amounts of from about 1% to about by weight, are satisfactory with the preferred quantity varying from 2% to 6%. The catalyst is usually applied to the textile from an aqueous or non-aqueous solvent either in combination with the mixture condensation product or separately. In addition to the catalyst, finishing agents such as whiteners, water repellents, softeners, and the like can be added to the textile treating solution.

As was mentioned previously, the cellulosic textile material treated with the mixed condensation product is heated for a brief time in order to effect the crosslinking reaction. The temperature utilized in this operation may vary from about 80 C. to about 200 C. for from about 10 minutes to a few seconds. Exposure of the treated textile for a few seconds at much higher temperatures (approximately 300 C.) can also be used if an extremely rapid reaction is desired. The heat treatment may be carried out in a forced draft oven, by steam, or by any other convenient method. After the heat treatment, the textile material is washed in order to remove catalyst and other residual soluble material and is then dried by conventional means.

The alkali catalyzed treatment of cellulosic textiles according to the present invention can be combined with a dyeing step wherein reactive dyes are utilized. Since reactive dyes are usually applied to and reacted with cellulose in the presence of alkali, the new reagents are particularly suitable whenever the objective is a simultaneous dyeing and finishing process.

The treating agent of this invention can be employed with textile materials formed either completely from cellulose fiber-containing materials, such as cotton, rayon, linen and the like, or blends thereof with other natural and synthetic fibers, such :as wool, nylon, polyesters, acrylics, polyolefins and the like, providing that the cellulosic component comprises at least 30%, by Weight, of the total fiber Weight. The treating agents can be applied at any stage of textile manufacture, namely, fibers, yarns, fabrics or garments. Moreover, the treatment of the inrials, as well as to non-woven assemblies.

In the following examples, which further illustrate the embodiments of this invention, all parts given are by weight unless otherwise indicated. The test methods referred to in the examples are as follows:

4 Crease recovery: ASTM-D129560T (in degrees) Tensile strength: Ravel Strip Method-ASTM-D1682- 59T (lbs.) Tear strength: ASTM-D1424-63 (lbs.) Abrasion resistance:

Stoll Flex Abrader, /2 lb. head, 2 lbs. toggle; ASTM-D1175-61T (in cycles) Damage due to Retained chlorine:

strength lost) Wash and wear: 'AATCC 88A-1964T (wash/wear rating) Whiteness: AATCC 110-1964T Laundering: Samples laundered in automatic hometype agitator washing machine at 60 C. for the full cycle (FAB detergent), 510 lbs. load. Samples flat bed pressed or tumble dried (TD) as indicated. Formaldehyde analysis: S. Siggia and E. Segal, Anal.

Chem. 25 640 (1953) EXAMPLE 1 The pH of a mixture of 232 g. (4 moles) of acetone, of 356 g. (4 moles), of ethylcarbamate and of 1296 g. (16 moles) of 37% aqueous formaldehyde solution was adjusted to 10 with 5 N sodium hydroxide. The alkaline reaction mixture was heated to 50 C. At this temperature, the reaction became exothermic. After each 2-hour period of heating, the pH of the mixture was readjusted to 10 with 5 N NaOH. After a total heating time of 7 hours the free formaldehyde content of the reaction mixture was 6.3 moles, indicating that 60.5% of the formaldehyde present had reacted. The reaction mixture was then neutralized with acetic acid to a pH of 6.8 and stripped in vacuo to a residue weight of 970 g. The crude product obtained was a viscous syrup, Which contained only 2% water as determined by the Karl Fisher method.

AATCC-924962 (percent EXAMPLE 2 The pH of a mixture of 174 g. (3 moles) of acetone, of 267 g. (3 moles) of ethylcarbamate, and of 1460 g. (18 moles) of 37% aqueous formaldehyde solution was adjusted to 10.0 with 5 N sodium hydroxide. The alkaline reaction mixture was heated at 55-50 C. for 12 hours. At intervals of 4 hours, the pH Was readjusted to 10 with 5 N NaOH. After a total heating time of 12 hours, 40% conversion was achieved as determined from the residual free formaldehyde content of the reaction mixture. The reaction mixture was then neutralized to a pH of 6.9 with a few drops of acetic acid and stripped to 848 g. weight in vacuo. The crude product obtained was a viscous syrup which contained only 0.3% water as determined by the Karl Fisher method.

EXAMPLE 3 Samples of plain weave cotton? fabric (commonly known as x 80 print cloth) were treated with a 15% act1ve aqueous solution of the product of Example 1, to which there were added 3.8% of potassium bicarbonate. The treatment was carried out on a laboratory padder setting the squeeze rolls at such a pressure as to give -1-06% wet pickup. The samples so treated were dried at 60 C. and then cured under the conditions specified below in a forced draft oven. After curing, the samples were neutralized in dilute acetic acid solution, washed in a non-ionic detergent solution at 60 C. and dried. The samples were conditioned overnight in a suitable atmosphere (21 C., 65% RH) and weighed on an analytical balance to determine the weight increase due The physical properties of the treated samples were as follows:

Recovery from creasing caused by retained Wet Example 3 was repeated, but instead of the product of Example 1, the product of Example 2 was used. The results were as follows:

Sample Curing conditions Percent wt. gain Percent N 1 135 0., 5 min 9. 5 0.65 2 163 C., 15 min 9. 2

The physical properties of the treated samples were as Percent damage poor crease recovery and excessive chlorine damage; the sample treated with DMA only (Sample B) exhibits excessive loss of whiteness, while samples treated with the product of Example 1 or with mixtures of DMEC and DMA give satisfactory performance results.

Any departure from the above description which conforms to the present invention is intended to be included within the scope of the invention as defined by the following claims:

What is claimed is:

1. The modification of a cellulose containing textile which comprises reacting said textile under conditions of alkaline catalysis at temperatures in excess of about 80 C. with a solution containing about 3 to about 30% based on the weight of said textile of an aldehydecarbamate-ketone condensate produced by the reaction of:

(1) formaldehyde,

(2) a ketone having the formula follows: CHPCFR Recovery from creasing Percent damage caused by retained where R is a lower alkyl group having 1 to 4 carbon Sample Dry chlorine atoms 9 1 263 261 10 (3) an alkyl carbamate having the formula 2 269 258 15 R--OFNH2 EXAMPLE 5 Example 3 was repeated, but for comparative purposes wherein R is an alkyl, hydroxyalkyl or alkoxy alkyl the chtfmlcals Wfire a,a"dlmethylolacetofle, (D group having no more than 6 carbon atoms at a tem- N,N-d1methylol ethyl carbamate (DMEC) and mixtures at of fro 0 to 80 C, at a pH of from 8 to 12 of these two reagents were applied in the presence of for a period of 1 to 24 hours wherein the initial potassium bicarbonate in addition to the mixed product mole ratio of formaldehyde to each mole of ketone prepared as described 1n Example 1. and carbamate is at least 2 to 3.

Percent Percent reagent DMEC applied OWF' reacted Product of Percent Percent (Calcd. from Sample DMEC DMA Example 1 W. G. Found percent N) A 15 4.9 0.67 5.4 B 12.3 0 o c 9.6 0. 48 3.9 1) 6.8 0. 49 4.0 E 7.5 7.4 0.38 3.0 F 8.8 0.28 2.4

*OWF--on weight of fabric.

All the above samples were cured at 135 C. for 2 minutes.

The physical properties of the treated samples were 50 2. A cellulose containing textile material impregnated with the condensation product of claim 1.

3. The method of treating a cellulose containing textile as follows:

Recovery Wash/wear rating Percent shrinkage irom creasing after 5L Whiteness TD after Sample Dry Wet 5L 3 10L W F Orig. 10L

A 203 186 1. 5 1. 5 1. 0 2. 0 69 63 B 262 266 3. 3 3. 5 0. 5 1. 0 39 43 C 260 256 3. 3 3. 5 0. 5 l. 5 44 62 D 243 249 2. 8 2. 8 0. 5 1. 5 57 56 E 245 257 2. 8 3. 0 0. 5 1. 5 56 F 265 266 3. 3 3. 3 0. 5 1. 0 53 59 Untr. control. 187 164 1. 0 1. 0 6. 5 5. 5 61 1 TD-Tumble drying. 2 Llaunderings.

The strength of the above samples was as follows:

Percent dam- 65 formula age caused by Tear Flex retained Str. W Abr. W chlorine 1. 1 200 None It only in presence of alkaline catalyst (Sample A) exhibits 75 having no more than 6 carbon atoms, the initial mole is apparent that the sample treated with DMEC where R is an alkyl, hydroxy alkyl, or alkoxy alkyl group ratio of said formaldehyde to each mole of ketone and carbamate being at least 2 to 3, and said solution containing about 3% toabout 30% based on the weight of said textile of said aldehyde-carbamate-ketone reagents, maintaining said impregnated material under conditions of alkaline catalysis at a temperature of less than about 80 C. at a pH of from 8 to 12 for a period of 1 to 24 hours, and thereafter drying and curing said impregnated material under conditions of alkaline catalysis and at a temperature in excess of about 80 C.

References Cited UNITED STATES PATENTS 3,144,299 8/ 1964 Frick-et a1 8116.3 3,416,880 12/1968 Kullrnan et al, 8-116.3

GEORGE F. LESMES, Primary Examiner J. CANNON, Assistant Examiner US. Cl. X.R.

P0405) UNITED STATES PATENT OFFICE (5/69) CERTIFICATE OF CORRECTION Patent No; Dated March 31 1970 lnventofls) Giuliana C. Tesoro It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column -3, line 36, "mixture condensation product" should read mixed condensation product Column 3, lines 70 and 71 "the treatment of the inrials, as well" should read -the treatment of the invention is applicable to woven and knitted textile materials, as well Column 4, line 44 "55-50%." should read -556O C. Column 4, bottom of the page Curing Conditions 135C. min. 163C. min. should read Curinq Conditions 135C. 5 min. l63 C., 5 min.

Signed and sealed this 12th day of September 1972.

(SEAL) Attest:

EDWARD M.F'LETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents 

